US7521578B2 - Process for the preparation of (meth)acrylates of tetra- or polyhydric alcohols - Google Patents
Process for the preparation of (meth)acrylates of tetra- or polyhydric alcohols Download PDFInfo
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- US7521578B2 US7521578B2 US11/995,406 US99540606A US7521578B2 US 7521578 B2 US7521578 B2 US 7521578B2 US 99540606 A US99540606 A US 99540606A US 7521578 B2 US7521578 B2 US 7521578B2
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- process according
- meth
- alkanol
- formula
- catalyst
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 150000005846 sugar alcohols Polymers 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 13
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 239000011541 reaction mixture Substances 0.000 claims abstract description 8
- -1 acrylic ester Chemical class 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 claims description 2
- UNXHWFMMPAWVPI-QWWZWVQMSA-N D-threitol Chemical compound OC[C@@H](O)[C@H](O)CO UNXHWFMMPAWVPI-QWWZWVQMSA-N 0.000 claims description 2
- 239000004386 Erythritol Substances 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- JVWLUVNSQYXYBE-UHFFFAOYSA-N Ribitol Natural products OCC(C)C(O)C(O)CO JVWLUVNSQYXYBE-UHFFFAOYSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims description 2
- 235000019414 erythritol Nutrition 0.000 claims description 2
- 229940009714 erythritol Drugs 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- HEBKCHPVOIAQTA-ZXFHETKHSA-N ribitol Chemical compound OC[C@H](O)[C@H](O)[C@H](O)CO HEBKCHPVOIAQTA-ZXFHETKHSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 4
- 125000005397 methacrylic acid ester group Chemical group 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 8
- 0 *OC(=O)C([1*])=C Chemical compound *OC(=O)C([1*])=C 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- UFLXKQBCEYNCDU-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CC(C)(C)NC(C)(C)C1 UFLXKQBCEYNCDU-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- DDPGLQRMAQYQEQ-UHFFFAOYSA-N 1-butoxypropyl 2-methylprop-2-enoate Chemical compound CCCCOC(CC)OC(=O)C(C)=C DDPGLQRMAQYQEQ-UHFFFAOYSA-N 0.000 description 1
- WIWZLDGSODDMHJ-UHFFFAOYSA-N 1-ethoxybutyl 2-methylprop-2-enoate Chemical compound CCCC(OCC)OC(=O)C(C)=C WIWZLDGSODDMHJ-UHFFFAOYSA-N 0.000 description 1
- HVBADOTWUFBZMF-UHFFFAOYSA-N 1-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOC(C)OC(=O)C(C)=C HVBADOTWUFBZMF-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- DJKKWVGWYCKUFC-UHFFFAOYSA-N 2-butoxyethyl 2-methylprop-2-enoate Chemical compound CCCCOCCOC(=O)C(C)=C DJKKWVGWYCKUFC-UHFFFAOYSA-N 0.000 description 1
- SFPNZPQIIAJXGL-UHFFFAOYSA-N 2-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOCCOC(=O)C(C)=C SFPNZPQIIAJXGL-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- XOIZPYZCDNKYBW-UHFFFAOYSA-N 5-tert-butylbenzene-1,3-diol Chemical compound CC(C)(C)C1=CC(O)=CC(O)=C1 XOIZPYZCDNKYBW-UHFFFAOYSA-N 0.000 description 1
- NUXLDNTZFXDNBA-UHFFFAOYSA-N 6-bromo-2-methyl-4h-1,4-benzoxazin-3-one Chemical compound C1=C(Br)C=C2NC(=O)C(C)OC2=C1 NUXLDNTZFXDNBA-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- QPUXWAKDRUWGSD-UHFFFAOYSA-N C=C(C(ON)=O)N Chemical compound C=C(C(ON)=O)N QPUXWAKDRUWGSD-UHFFFAOYSA-N 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- IPPWILKGXFOXHO-UHFFFAOYSA-N chloranilic acid Chemical compound OC1=C(Cl)C(=O)C(O)=C(Cl)C1=O IPPWILKGXFOXHO-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- XRXPHPJRVWEWKQ-UHFFFAOYSA-N cyclohexyloxymethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCOC1CCCCC1 XRXPHPJRVWEWKQ-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- WMAFNLQQGPUKCM-UHFFFAOYSA-N ethoxymethyl 2-methylprop-2-enoate Chemical compound CCOCOC(=O)C(C)=C WMAFNLQQGPUKCM-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- DWXAVNJYFLGAEF-UHFFFAOYSA-N furan-2-ylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CO1 DWXAVNJYFLGAEF-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001427 mPEG Polymers 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XGRBZUSXGVNWMI-UHFFFAOYSA-N phenylmethoxymethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCOCC1=CC=CC=C1 XGRBZUSXGVNWMI-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
Definitions
- the invention relates to a process for transesterifying (meth)acrylic esters with especially polyfunctional alkanols using a catalyst.
- di- and triorganotin compounds effectively catalyse esterification and transesterification reactions of (meth)acrylic acid and (meth)acrylic esters.
- the advantageous effects of the catalysts described there include high catalytic activity, low tendency to dehydration, especially of secondary alcohols, and high ester yields.
- EP 663386 describes a process for transesterifying (meth)acrylic esters with especially polyfunctional alkanols using a mixed catalyst consisting of diorganyltin oxide and organyltin halide.
- EP 663386 specifies a reaction time of 14 hours for preparing pentaerythrityl tetramethacrylate. In addition, only 78 mol % of pentaerythrityl tetramethacrylate is isolated.
- the object is achieved by a process for preparing acrylic and methacrylic esters by transesterifying (meth)acrylic esters of the formula I:
- R 1 is H or CH 3 and R 2 is an alkyl radial having 1 to 6 carbon atoms with alkanols which have four or more esterifiable hydroxyl groups, characterized in that the transesterification catalyst used is 0.01 to 10% by weight, based on the entire reaction mixture, of lithium amide catalysts.
- the notation (meth)acrylate represents the esters of (meth)acrylic acid and here means both methacrylate, for example methyl methacrylate, ethyl methacrylate, etc., and acrylate, for example methyl acrylate, ethyl acrylate, etc., and mixtures of the two.
- catalysts from the group of the lithium amides can be used preferentially.
- the alkanols used in the transesterification preferably have four or more esterifiable hydroxyl groups, for example pentaerythritol, erythritol or threitol.
- R′′′ is an unbranched or branched, aliphatic or aromatic radical having 4 to 40 carbon atoms.
- Examples of representatives of penta- and hexafunctional alkanols which can be used as transesterification components include: arabinitol, ribitol, xylitol, sorbitol, glucitol and mannitol, all known as sugar alcohols (cf., for example, Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol. 1, pages 754 to 789, John Wiley, New York, 1978).
- the acrylic or methacrylic esters of the formula I used may, for example, be: alkyl (meth)acrylates of straight-chain, branched or cycloaliphatic alcohols having from 1 to 40 carbon atoms, for example, methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, i-butyl(meth)acrylate, tert-butyl(meth)acrylate, pentyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, stearyl(meth)acrylate, lauryl(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate; aryl(meth)acrylates, for example benzyl(meth)acrylate or phenyl(meth)acrylate, each of which may have unsubstituted or mono- to tetrasubstituted
- the reaction of acrylic or methacrylic esters of the formula I with the tetra- or polyfunctional alkanols is carried out in the presence of 0.01 to 10% by weight of catalyst, preferably of 0.1 to 5% by weight, more preferably of 0.2 to 2% by weight of catalyst, based on the overall reaction mixture.
- the reaction of acrylic or methacrylic esters of the formula I with the tetra- or polyfunctional alkanols is carried out at temperatures between 30 and 180° C., preferably between 50 and 130 degrees in the presence of 0.01 to 10% by weight, preferably of 0.1 to 5% by weight, more preferably of 0.2 to 2% by weight, based on the overall reaction mixture, of the lithium amide catalyst.
- the process may be carried out in any inert aprotic solvent. Preference is given to aliphatic or aromatic solvents, particular preference to xylene, toluene or cyclohexane.
- inhibitors which prevent free-radical polymerization of the (meth)acrylic groups during the reaction may be added. These inhibitors are widely known in the technical field.
- R 6 is a linear or branched alkyl radical having one to eight carbon atoms, halogen or aryl, preferably an alkyl radical having one to four carbon atoms, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, Cl, F or Br;
- o is an integer in the range from one to four, preferably one or two;
- R 7 is hydrogen, a linear or branched alkyl radical having one to eight carbon atoms or aryl, preferably an alkyl radical having one to four carbon atoms, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
- R 6 and o are each as defined above.
- Phenols of the general structure (V) are likewise used
- R 8 is a linear or branched alkyl radical having one to eight carbon atoms, aryl or aralkyl, propionic esters with mono- to tetrahydric alcohols which may also contain heteroatoms such as S, O and N, preferably an alkyl radical having one to four carbon atoms, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.
- a further advantageous class of substances is that of hindered phenols based on triazine derivatives of the formula (VI)
- R 10 C p H 2p+1
- the content of the inhibitors is generally 0.01-0.50% (wt./wt.), the concentration of the inhibitors preferably being selected such that the colour number to DIN 55945 is not impaired. Many of these inhibitors are commercially available.
- (Meth)acrylic esters of the formula I and hydroxyl groups of the tetra- or polyfunctional alkanols react to give the desired end products.
- the (meth)acrylic esters I it is appropriate to keep the (meth)acrylic esters I in excess during the reaction, the (meth)acrylic acid I being used in amounts of 1.2 to 15 mol, preferably 2 to 10 mol, per mole of hydroxyl groups.
- the reaction can be carried out under standard pressure, reduced pressure or elevated pressure, and can be conducted batchwise or continuously.
- the reactants (meth)acrylic ester I and tetra- or polyfunctional alkanol are heated to reaction temperature together in the presence of the lithium amide catalyst, and the eliminated alkanol R 2 OH and the excess (meth)acrylic ester I are distilled off continuously, preferably together in an azeotrope.
- the reaction times are generally between 1 and 20 hours, preferably between 2 and 8 hours, and depend upon the reaction temperature or upon the amount of catalyst used. It is also possible to carry out the reaction in the presence of an inert solvent, for example toluene, or cyclohexane.
- the excess (meth)acrylic ester I is removed from the reaction product partly or preferably fully, for example by distilling it off. Subsequently, the removal of the catalyst is effected by filtration.
- the tetra- or polyfunctional (meth)acrylic esters are outstanding copolymers for reactions in which crosslinking is desired during the polymerization.
- they are used in coatings, dental applications, adhesives, in vulcanization or radiative curing.
- the batch is introduced into the reaction apparatus and dewatered, then the batch is cooled. At approx. 80° C., lithium amide is added and the reaction temperature is increased again.
- the methanol formed is distilled as the MMA/methanol azeotrope through a column head. Once the column head temperature no longer falls, the reaction is ended after a reaction time of 6.7 h and at a reaction temperature of 101° C. to 113° C.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005044250.1 | 2005-09-15 | ||
| DE102005044250A DE102005044250A1 (de) | 2005-09-15 | 2005-09-15 | Verfahren zur Herstellung von Methacrylaten mit reaktiven Doppelbindungen |
| PCT/EP2006/065366 WO2007031384A1 (de) | 2005-09-15 | 2006-08-16 | Verfahren zur herstellung von (meth) acrylaten vier- oder mehrwertiger alkohole |
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| US20080194861A1 US20080194861A1 (en) | 2008-08-14 |
| US7521578B2 true US7521578B2 (en) | 2009-04-21 |
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| US11/995,406 Expired - Fee Related US7521578B2 (en) | 2005-09-15 | 2006-08-16 | Process for the preparation of (meth)acrylates of tetra- or polyhydric alcohols |
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| Country | Link |
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| US (1) | US7521578B2 (de) |
| EP (1) | EP1924547A1 (de) |
| JP (1) | JP5080473B2 (de) |
| KR (1) | KR101297448B1 (de) |
| CN (1) | CN101203478B (de) |
| AU (1) | AU2006290941B2 (de) |
| BR (1) | BRPI0615874A2 (de) |
| CA (1) | CA2622353C (de) |
| DE (1) | DE102005044250A1 (de) |
| MX (1) | MX2008003169A (de) |
| NZ (1) | NZ564132A (de) |
| RU (1) | RU2446144C2 (de) |
| WO (1) | WO2007031384A1 (de) |
| ZA (1) | ZA200802414B (de) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080287629A1 (en) * | 2006-02-09 | 2008-11-20 | Evonik Roehm Gmbh | Aqueous N-Methylolmethacrylamide-Methacrylamide Mixture |
| US8686181B2 (en) | 2007-07-05 | 2014-04-01 | Evonik Roehm Gmbh | Method for producing ethylene glycol dimethacrylate |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10314776A1 (de) * | 2003-03-31 | 2004-10-14 | Rohmax Additives Gmbh | Schmierölzusammensetzung mit guten Reibeigenschaften |
| DE102004021717A1 (de) * | 2004-04-30 | 2005-11-24 | Rohmax Additives Gmbh | Verfahren zur Herstellung von Schmierfett |
| DE102004034618A1 (de) * | 2004-07-16 | 2006-02-16 | Rohmax Additives Gmbh | Verwendung von Pfropfcopolymeren |
| DE102004037929A1 (de) * | 2004-08-04 | 2006-03-16 | Rohmax Additives Gmbh | Verfahren zur radikalischen Polymerisation ethylenisch-ungesättigter Verbindungen |
| DE102006039420A1 (de) | 2006-08-23 | 2008-02-28 | Evonik Rohmax Additves Gmbh | Verfahren zur Herstellung von Methacrylatestern |
| JP2008100972A (ja) * | 2006-10-20 | 2008-05-01 | Kuraray Medical Inc | 親水性単量体の製造方法 |
| WO2012160007A1 (de) | 2011-05-24 | 2012-11-29 | Evonik Röhm Gmbh | Reaktivharze für kabelvergussmassen |
| DE102011081649A1 (de) | 2011-08-26 | 2013-02-28 | Evonik Röhm Gmbh | Längerkettige Methacrylate aus nachwachsenden Rohstoffen |
| WO2015099915A1 (en) * | 2013-12-26 | 2015-07-02 | Dow Global Technologies Llc | Inhibitor combination for lithium salt-catalyzed transesterification process and method for removing lithium salt |
| EP3133058B1 (de) * | 2014-04-16 | 2019-05-29 | Toagosei Co., Ltd. | Herstellungsverfahren für multifunktionelles (meth)acrylat |
| JP6789231B6 (ja) | 2015-02-26 | 2020-12-16 | ビーエイエスエフ・ソシエタス・エウロパエアＢａｓｆ Ｓｅ | イソソルビドジ（メタ）アクリラートを製造する方法 |
| WO2017002961A1 (ja) * | 2015-07-02 | 2017-01-05 | 東亞合成株式会社 | 硬化型組成物 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0151368A2 (de) | 1983-12-22 | 1985-08-14 | Ciba-Geigy Ag | Verfahren zur Herstellung eines Hydroxyphenylcarbonsäureesters |
| DE3423443A1 (de) | 1984-06-26 | 1986-01-02 | Röhm GmbH, 6100 Darmstadt | Verfahren zur herstellung von estern der acryl- und methacrylsaeure durch umesterung |
| EP0663386A1 (de) | 1994-01-17 | 1995-07-19 | Röhm GmbH | Verfahren zur Umesterung von (Meth)acrylsäureestern |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2364126A1 (de) * | 1972-12-27 | 1974-07-11 | Ciba Geigy Ag | Verfahren zur herstellung von hydroxyalkylphenylderivaten |
| DE2744641B2 (de) * | 1977-10-04 | 1979-08-02 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Verfahren zur Herstellung von Estern der Methacrylsäure |
| US5136082A (en) * | 1990-08-03 | 1992-08-04 | Himont Incorporated | Process for preparing organic esters and amides and catalyst system therefor |
| JP3460259B2 (ja) * | 1992-09-18 | 2003-10-27 | 株式会社エーピーアイ コーポレーション | ペンタエリスリトールエステル化合物およびその用途 |
| JPH0931018A (ja) * | 1995-07-24 | 1997-02-04 | Dainippon Ink & Chem Inc | ペンタエリスリトール（メタ）アクリルエステル類の製造法 |
| JP2000302749A (ja) * | 1999-04-26 | 2000-10-31 | Hitachi Chem Co Ltd | （メタ）アクリル酸ポリオキシエチレン化ビスフェノ−ルｓエステル、その製造法及び感光性樹脂組成物 |
| JP4826026B2 (ja) * | 2001-05-18 | 2011-11-30 | 日立化成工業株式会社 | （メタ）アクリル酸エステルの製造法 |
| JP2005213218A (ja) * | 2004-01-30 | 2005-08-11 | Hitachi Chem Co Ltd | ポリオキシアルキレン化グリコール類の（メタ）アクリル酸エステル誘導体の製造方法 |
-
2005
- 2005-09-15 DE DE102005044250A patent/DE102005044250A1/de not_active Withdrawn
-
2006
- 2006-08-16 AU AU2006290941A patent/AU2006290941B2/en not_active Ceased
- 2006-08-16 KR KR1020087006385A patent/KR101297448B1/ko not_active IP Right Cessation
- 2006-08-16 WO PCT/EP2006/065366 patent/WO2007031384A1/de active Application Filing
- 2006-08-16 NZ NZ564132A patent/NZ564132A/en not_active IP Right Cessation
- 2006-08-16 EP EP06792846A patent/EP1924547A1/de not_active Withdrawn
- 2006-08-16 BR BRPI0615874-9A patent/BRPI0615874A2/pt not_active Application Discontinuation
- 2006-08-16 MX MX2008003169A patent/MX2008003169A/es active IP Right Grant
- 2006-08-16 JP JP2008530456A patent/JP5080473B2/ja not_active Expired - Fee Related
- 2006-08-16 RU RU2008114030/04A patent/RU2446144C2/ru not_active IP Right Cessation
- 2006-08-16 US US11/995,406 patent/US7521578B2/en not_active Expired - Fee Related
- 2006-08-16 CA CA2622353A patent/CA2622353C/en not_active Expired - Fee Related
- 2006-08-16 CN CN2006800220452A patent/CN101203478B/zh not_active Expired - Fee Related
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- 2008-03-14 ZA ZA200802414A patent/ZA200802414B/xx unknown
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| EP0151368A2 (de) | 1983-12-22 | 1985-08-14 | Ciba-Geigy Ag | Verfahren zur Herstellung eines Hydroxyphenylcarbonsäureesters |
| DE3423443A1 (de) | 1984-06-26 | 1986-01-02 | Röhm GmbH, 6100 Darmstadt | Verfahren zur herstellung von estern der acryl- und methacrylsaeure durch umesterung |
| EP0663386A1 (de) | 1994-01-17 | 1995-07-19 | Röhm GmbH | Verfahren zur Umesterung von (Meth)acrylsäureestern |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080287629A1 (en) * | 2006-02-09 | 2008-11-20 | Evonik Roehm Gmbh | Aqueous N-Methylolmethacrylamide-Methacrylamide Mixture |
| US8057698B2 (en) | 2006-02-09 | 2011-11-15 | Evonik Röhm Gmbh | Aqueous N-methylolmethacrylamide-methacrylamide mixture |
| US8686181B2 (en) | 2007-07-05 | 2014-04-01 | Evonik Roehm Gmbh | Method for producing ethylene glycol dimethacrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0615874A2 (pt) | 2011-05-31 |
| CA2622353A1 (en) | 2007-03-22 |
| DE102005044250A1 (de) | 2007-03-29 |
| CA2622353C (en) | 2014-04-15 |
| JP5080473B2 (ja) | 2012-11-21 |
| AU2006290941B2 (en) | 2012-06-14 |
| RU2446144C2 (ru) | 2012-03-27 |
| NZ564132A (en) | 2011-04-29 |
| KR101297448B1 (ko) | 2013-08-16 |
| CN101203478A (zh) | 2008-06-18 |
| CN101203478B (zh) | 2011-05-04 |
| WO2007031384A1 (de) | 2007-03-22 |
| US20080194861A1 (en) | 2008-08-14 |
| KR20080044301A (ko) | 2008-05-20 |
| EP1924547A1 (de) | 2008-05-28 |
| JP2009507881A (ja) | 2009-02-26 |
| ZA200802414B (en) | 2009-01-28 |
| RU2008114030A (ru) | 2009-10-20 |
| AU2006290941A1 (en) | 2007-03-22 |
| MX2008003169A (es) | 2008-03-18 |
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